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Supporting Information for
Strategic Design of Triphenylamine- and Triphenyltriazine-Based Two-Dimensional Covalent Organic Frameworks for CO2 Uptake and Energy Storage
Ahmed F. M. EL-Mahdy,a,b Cheng-Han Kuo,a Abdulmohsen Alshehri,c Christine Young,d Yusuke Yamauchi,e,f Jeonghun Kim*e and Shiao-Wei Kuo*a
a Department of Materials and Optoelectronic Science, National Sun Yat-Sen University, Kaohsiung 80424, Taiwan. E-mail: kuosw@faculty.nsysu.edu.tw
b Chemistry Department, Faculty of Science, Assiut University, Assiut 71516, Egypt.c Department of Chemistry, King Abdulaziz University, P.O. Box. 80203, Jeddah
21589, Saudi Arabiad International Centre for Materials Nanoarchitectonics (MANA), National Institute
for Materials Science (NIMS), 1-1 Namiki, Tsukuba, Ibaraki 305-0044, Japan.e School of Chemical Engineering and Australian Institute for Bioengineering and
Nanotechnology (AIBN), The University of Queensland, Brisbane, QLD 4072, Australia. E-mail: jeonghun.kim@uq.edu.au
f Department of Plant & Environmental New Resources, Kyung Hee University, 1732 Deogyeong-daero, Giheung-gu, Yongin-si, Gyeonggi-do 446-701, South Korea
Electronic Supplementary Material (ESI) for Journal of Materials Chemistry A.This journal is © The Royal Society of Chemistry 2018
2
Contents
Section A. Characterization
Section B. Materials
Section C. Synthetic procedures
Section D. NMR spectral profiles
Section E. ESI
Section F. FT-IR spectral profiles
Section G. Elemental analysis
Section H. TGA profiles
Section I. PXRD patterns
Section J. SEM analysis
Section K. CO2 isosteric heats of adsorption
Section L. Electrochemical analysis
3
Section A. Characterization
Proton and carbon nuclear magnetic resonance (1H and 13C NMR) spectra were recorded using
an INOVA 500 instrument with DMSO-d6 and CDCl3 as solvents and tetramethylsilane (TMS)
as the external standard. Chemical shifts are provided in parts per million (ppm). Fourier
transform mass spectra (electrospray ionization, ESI) of were recorded using a Bruker Solarix
spectrometer. FTIR spectra were recorded using a Bruker Tensor 27 FTIR spectrophotometer
and the conventional KBr plate method; 32 scans were collected at a resolution of 4 cm–1. Solid
state nuclear magnetic resonance (SSNMR) spectra were recorded using a Bruker Avance 400
NMR spectrometer and a Bruker magic angle spinning (MAS) probe, running 32,000 scans.
Cross-polarization with MAS (CPMAS) was used to acquire 13C NMR spectral data at 75.5
MHz. The CP contact time was 2 ms; 1H decoupling was applied during data acquisition. The
decoupling frequency corresponded to 32 kHz. The MAS sample spinning rate was 10 kHz.
Elemental analysis (EA) was performed using an Elementar vario EL III apparatus. Powder X-
ray diffraction (PXRD) was carried out with a Siemens D5000 using monochromated
. The sample was spread in a thin layer on the square recess of an XRD Cu/Kα (λ = 0.1542 nm)
sample holder. Field emission scanning electron microscopy (FE-SEM) was conducted using a
JEOL JSM-7610F scanning electron microscope. Samples were treated via Pt sputtering for
100 s prior to observation. BET surface area and porosimetry measurements of the prepared
samples (ca. 20–100 mg) were performed using a Micromeritics ASAP 2020 Surface Area and
Porosity analyzer. Nitrogen isotherms were generated through incremental exposure to
ultrahigh-purity N2 (up to ca. 1 atm) in a liquid nitrogen (77 K) bath. Carbon dioxide isotherms
were generated using ultrahigh-purity CO2 (to ca. 900 mmHg) in a water bath (295 K). Surface
parameters were determined using BET adsorption models in the instrument’s software. TGA
was performed using a TA Q-50 analyzer under a flow of N2 atmosphere. The samples were
sealed in a Pt cell and heated from 40 to 800 °C at a heating rate of 20 °C min–1 under a flow
of N2 atmosphere at a flow rate of 50 mL min–1. Molecular modeling was performed using
Reflex, a software package for crystal determination from XRD patterns, implemented in MS
modeling (v. 4.4, Accelrys). Unit cell dimensions were first manually determined from the
observed XRD peak positions using the coordinates. The space group for the hexagonal crystal
system was selected as P3.
For electrochemical measurement, the electrodes were prepared by coating slurries
containing a COF powder (1 mg, 65 wt.%), a conducting agent (Super-P, 25 wt.%), and
poly(vinylidene fluoride) binder (PVDF, 10 wt.%) dissolved in N-methyl-2-pyrrolidone
(NMP)—on a carbon paper electrode. The electrodes were dried at 100 °C for 12 h in a vacuum
4
oven. The electrochemical measurements were performed using an electrochemical workstation
(CHI 660e, CH Instruments). For the three-electrode measurements, Ag/AgCl was used as the
reference electrode and a Pt wire electrode as the counter electrode. All electrochemical
measurements were performed using 0.5 M H2SO4 as the aqueous electrolyte. Gravimetric
capacitances were calculated using the galvanostatic charge/discharge method and the
following equation:
𝐶𝑔 =𝐼 × ∫𝑉 𝑑𝑡
𝑀 × ∆𝑉2
where Cg is the gravimetric capacitance (F g–1), ΔV is the potential window, I is the current (A),
t is the discharge time, and M is the total mass of active materials (in grams).
5
Section B. Materials
1-Fluoro-4-nitrobenzene (99%), trifluoromethanesulfonic acid ( 98%), 4-bromoacetophenone ≥
( 98%), 4-bromobenzaldehyde ( 98%), and 4-bromobenzonitrile ( 98%) were purchased ≥ ≥ ≥
from Alfa Aesar. Palladium on activated carbon (10% Pd, unreduced), triphenylamine (99%),
N-formylpiperidine (99%), and mesitylene (99%) were purchased from Acros. 4-Nitroaniline
(99%) was purchased from Fluka. 4-Aminobenzonitrile (98%) was purchased from Matrix
Scientific. n-Butyllithium (2.5 M in hexane) was purchased from Albemarle.
6
Section C. Synthetic procedures
Tris(4-nitrophenyl)amine (TPA-3NO2)
NO2
NH2
F
NO2
N
NO2
O2N NO2
K2CO3
DMSO+
1-Fluoro-4-nitrobenzene (8 mL, 0.08 mmol) was added to a suspension of 4-nitroaniline (5.00
g, 36.2 mmol) and K2CO3 (30 g) in dry DMSO (40 mL) in a 100-mL two-neck bottle under a
flow of N2. The mixture was heated at 120 °C for 48 h and then the solvent was removed under
vacuum. The formed solid was suspended in methanol and collected via vacuum filtration. The
compound was washed with H2O and methanol. The product was dried under vacuum overnight
to yield a yellow solid of TPA-3NO2. FT-IR (powder): 1582, 1508, 1338, 1314, 1270, 1180,
1110, 849, 749, 703, 692, 676, 506 cm-1. 1H NMR (DMSO-d6, 25 °C, 600 MHz): = 8.26 (d, J 𝛿
= 12 Hz, 6H), 7.36 (d, J = 10.8 Hz, 6H). 13C NMR (DMSO-d6, 25 °C, 500 MHz): 150.83,
143.55, 125.77, 124.90.
Tris(4-aminophenyl)amine (TPA-3NH2)
N
NO2
O2N NO2
H2N NH2
1, 4-Dioxane/EthanolN
NH2
H2N NH2
A suspension of tris(4-nitrophenyl)amine (10.0 g, 26.3 mmol) and palladium on activated
carbon (0.658 g, 0.006 mmol) in dry 1,4-dioxane (46 mL) and EtOH (23 mL) was heated at 80
°C for 1 h in a 250-mL two-neck bottle under a flow of N2 and then hydrazine monohydrate
(26.3 mL, 0.84 mmol) was added. The mixture was heated at 80 °C for 48 h. Palladium on
activated carbon was removed via vacuum filtration. The product was crystallized at low
temperature. The precipitate was collected via vacuum filtration and dried under vacuum
overnight to yield a gray solid of TPA-3NH2. FT-IR (powder): 3406, 3334, 3207, 3034, 3003,
1620, 1504, 1328, 1259, 829, 568, 505 cm-1. 1H NMR (DMSO-d6, 25 °C, 600 MHz): = 6.58 𝛿
(s, 6H), 4.69 (s, 6H), 6.44 (d, J = 10.2 Hz, 6H). 13C NMR (DMSO-d6, 25 °C, 500 MHz): 143.17,
138.65, 124.08, 114.76.
7
2,4,6-Tris(4-aminophenyl)triazine (TPT-3NH2)
CN
NH2
Trif lic acidChloroform
NN
N
NH2
H2N NH2
A suspension of 4-aminobenzonitrile (1.5 g, 12.70 mmol) in dry CHCl3 (20 mL) in a 100-mL
two-neck bottle was cooled in an ice bath under a flow of N2 and then trifluoromethanesulfonic
acid (4 mL, 0.045 mmol) was added. The mixture was stirred for 30 min in the ice bath and
then warmed to room temperature. After stirring for an additional 24 h at room temperature, ice
water was added. The aqueous suspension was neutralized by adding ammonium hydroxide.
The precipitate was collected via vacuum filtration and dried under vacuum overnight to yield
a white solid of TPT-3NH2. FT-IR (powder): 3460, 3379, 3321, 3207, 1633, 1606, 1579, 1498,
1433, 1367, 1309, 1180, 1147, 813, 590, 513 cm-1. 1H NMR (DMSO-d6, 25 °C, 600 MHz): = 𝛿
5.89 (s, 6H), 8.36 (d, J = 10.2 Hz, 6H), 6.70 (d, J = 10.2 Hz, 6H). 13C NMR (DMSO-d6, 25 °C,
500 MHz): 170.45, 153.77, 130.82, 123.56, 113.69.
Tris(4-formylphenyl)amine (TPA-3CHO)
N
POCl3
DMF N
CHO
OHC CHO
A suspension of triphenylamine (5.00 g, 20.4 mmol) in dry DMF (35 mL) in a 100-mL two-
neck bottle was cooled in an ice bath under a flow of N2 and then phosphoryl chloride (19 mL,
0.20 mmol) was added. The mixture was stirred for 30 min at room temperature and then heated
at 110 °C for 12 h. The product was poured into ice water and then the aqueous suspension was
neutralized through the addition of a NaOH solution. The aqueous phase was extracted with
DCM; the combined organic extracts were dried (anhydrous MgSO4) and filtered. The solvent
was removed under rotary evaporation and after column chromatography [silica gel, ethyl
acetate (EA): hexanes = 1:4] product was obtained as a yellow solid. FT-IR (powder): 2801,
2724, 1693, 1587, 1504, 1323, 1274, 1217, 1168, 819, 526 cm-1. 1H NMR (DMSO-d6, 25 °C,
600 MHz): = 9.93 (s, 3H), 7.89 (d, J = 10.2 Hz, 6H), 7.26 (d, J = 10.2 Hz, 6H). 13C NMR 𝛿
(DMSO-d6, 25 °C, 500 MHz): 191.49, 150.73, 132.19, 131.44, 124.43.
8
2,4,6-Tris(4-bromophenyl)pyridine (TPP-3Br)
Br
COCH3
+
CHO
Br
CH3COONH4
N
Br
Br BrAcetic acid
A 20-mL microwave vial equipped with a stirrer bar was charged with 4-bromoacetophenone
(4.14 g, 20.8 mmol), 4-bromobenzaldehyde (1.94 g, 10.4 mmol), ammonium acetate (28.0 g,
363 mmol), and acetic acid (14.6 mL, 0.260 mmol). The contents were heated in a microwave
oven under autogenous pressure at 500 W and 220 °C for 45 min. After cooling to room
temperature, deionized water was added. The aqueous suspension was neutralized through the
addition of a solution of NaHCO3. The aqueous phase was extracted with DCM; the combined
organic extracts were dried (anhydrous MgSO4) and filtered. The solvent was evaporated under
reduced pressure; the residue was recrystallized (acetone) and dried under vacuum overnight to
yield a white solid of TPP-3Br. FT-IR (powder): 1593, 1573, 1541, 1500, 1420, 1376, 1177,
1067, 1007, 813, 489 cm-1. 1H NMR (CDCl3, 25 °C, 600 MHz): 8.03 (d, J = 10.2 Hz, 2H), 7.57
(m, aromatic, 12H). 13C NMR (CDCl3, 25 °C, 500 MHz): 156.59, 149.38, 137.96, 137.50,
132.36, 131.91, 128.62, 123.80, 123.68, 116.75.
2,4,6-Tris(4-formylphenyl)pyridine (TPP-3CHO)
N
Br
Br BrN
CHO
OHC CHOTHF
N-formylpiperidine
n-BuLi
A suspension of 2,4,6-tris(4-bromophenyl)pyridine (1.00 g, 1.85 mmol) in dry THF (130 mL)
in a 250-mL two-neck bottle was cooled to –78 °C under a flow of N2 and then a solution of n-
BuLi (7.40 mL, 18.8 mmol, 2.5 M in hexane) was added. The mixture was stirred at –70 °C for
3 h and then N-formylpiperidine (2.20 mL, 19.9 mmol) was added. The mixture was stirred for
1 h at –78 °C and then warmed to room temperature. After stirring for an additional 16 h at
room temperature, 0.88 M HCl (40 mL) of was added. The aqueous phase was extracted with
DCM; the combined organic extracts were dried (anhydrous MgSO4) and filtered. The solvent
was evaporated under reduced pressure. The residue was purified using the centrifugation
method to yield a white solid of TPP-3CHO. FT-IR (powder): 2810, 2724, 1697, 1598, 1571,
1544, 1211, 856, 819, 792 cm-1. 1H NMR (CDCl3, 25 °C, 600 MHz): 10.06 (d, J = 4.8 Hz, 3H),
8.31 (d, J = 9.6 Hz, 2H), 7.85 (m, aromatic, 12H). 13C NMR (CDCl3, 25 °C, 500 MHz): 192.90,
9
192.52, 157.49, 150.35, 145.02, 144.80, 137.54, 137.47, 131.24, 130.92, 128.63, 128.41,
119.33.
2,4,6-Tris(4-bromophenyl)-1,3,5-triazine (TPT-3Br)
CN
Br
Trif lic acidChloroform
NN
N
Br
Br Br
A suspension of 4-bromobenzonitrile (1.50 g, 8.24 mmol) in dry CHCl3 (20 mL) in a 100-mL
two-neck bottle was cooled in an ice bath under a flow of N2 and then trifluoromethanesulfonic
acid (4 mL, 0.045 mmol) was added. The mixture was stirred for 30 min in the ice bath and
then warmed to room temperature. After stirring for an additional 20 h at room temperature, ice
water was added. The aqueous suspension was neutralized through the addition of ammonium
hydroxide. The precipitate was collected via vacuum filtration and dried under vacuum
overnight to yield a white solid of TPT-3Br. FT-IR (powder): 1578, 1518, 1400, 1372, 1173,
1069, 1011, 843, 806, 498 cm-1. 1H NMR (CDCl3, 25 °C, 600 MHz): 8.60 (d, J = 12 Hz, 6H),
7.71 (d, J = 12Hz, 6H). 13C NMR (CDCl3, 25 °C, 500 MHz): 171.10, 134.77, 132.01, 130.48,
127.84.
2,4,6-Tris(4-formylphenyl)triazine (TPT-3CHO)
NN
N
Br
Br Br
NN
N
CHO
OHC CHOTHF
N-formylpiperidine
n-BuLi
A suspension of 2,4,6-tris(4-bromophenyl)-1,3,5-triazine (1.00 g, 1.83 mmol) in dry THF (130
mL) in a 250-mL two-neck bottle was cooled to –78 °C under a flow of N2 and then a solution
of n-BuLi (7.30 mL, 18.6 mmol, 2.5 M in hexane) was added. The mixture was stirred at –70
°C for 3 h and then N-formylpiperidine (2.2 mL, 19.9 mmol) was added. The mixture was
stirred for 30 min at –78 °C and then warmed to room temperature. After stirring for an
additional 16 h at room temperature, 2.88 M HCl (50 mL) was added. The aqueous phase was
extracted with CHCl3; the combined organic extracts were dried (anhydrous MgSO4) and
filtered. The solvent was evaporated under reduced pressure. The residue was purified using
the centrifugation method to yield a white solid of TPT-3CHO. FT-IR (powder): 2821, 2729,
1706, 1583, 1517, 1419, 1357, 1298, 1201, 1105, 1012, 806, 499 cm-1. 1H NMR (CDCl3 and
10
DMSO-d6, 25 °C, 600 MHz): 10.12 (s, 3H), 8.89 (d, J = 9.6 Hz, 6H), 8.06 (d, J = 9.6Hz, 6H). 13C NMR (CDCl3, 25 °C, 500 MHz): 192.48, 171.47, 140.77, 139.46, 130.03, 129.80.
TPA-TPA-COF (TPA-COF-1)
N
NH2
H2N NH2
N
CHO
OHC CHO
N
N N
NN
NN
NN
NN
N
+
TPA-3NH2 TPA-3CHO
TPA-TPA-COF (TPA-COF-1)
A mixture of TPA-3NH2 (70.0 mg, 0.240 mmol), TPA-3CHO (79.4 mg, 0.240 mmol), acetic
acid (6 M, 1.2 mL) in 1,4-dioxane/mesitylene (5 mL/5 mL) in a Pyrex tube (25 mL) was
degassed using three freeze/pump/thaw cycles. The tube was sealed off under a flame and then
heated at 120 °C for 96h. After cooling to room temperature, the yellow precipitate was washed
several times with THF, MeOH, and acetone, respectively, and then dried under vacuum at 120
°C overnight to yield a yellow solid (87%).
TPA-TPP COF (TPA-COF-2)
N
NH2
H2N NH2
N
CHO
OHC CHO
N
N N
NN
NN
NN
NN
N
+
TPA-3NH2 TPP-3CHO
TPA-TPP COF (TPA-COF-2)
A mixture of TPA-3NH2 (70.0 mg, 0.240 mmol), TPP-3CHO (94.4 mg, 0.240 mmol), and acetic
acid (6 M, 1.2 mL) in 1,4-dioxane/mesitylene (5 mL/5 mL) in a Pyrex tube (25 mL) was
degassed using three freeze/pump/thaw cycles. The tube was sealed off under a flame and then
heated at 120 °C for 96 h. After cooling to room temperature, the yellow precipitate was washed
11
several times with THF, MeOH, and acetone, respectively, and then dried under vacuum at 120
°C overnight to yield a yellow solid (85%).
TPA-TPT COF (TPA-COF-3)
N
NH2
H2N NH2
NN
N
CHO
OHC CHO
+
N
N N
NN N
N NN
NN
NN
NN
N NN
TPA-3NH2
TPA-TPT COF (TPA-COF-3)
TPT-3CHO
A mixture of TPA-3NH2 (70.0 mg, 0.240 mmol), TPT-3CHO (94.8 mg, 0.240 mmol), and
acetic acid (6 M, 1.2 mL) in 1,4-dioxane/mesitylene (5 mL/5 mL) in a Pyrex tube (25 mL) was
degassed using three freeze/pump/thaw cycles. The tube was sealed off under a flame and then
heated at 120 °C for 96 h. After cooling to room temperature, the red precipitate was washed
several times with THF, MeOH, and acetone, respectively, and then dried under vacuum at 120
°C overnight to yield a red solid (88%).
TPT-TPA COF (TPT-COF-4)
NN
N
NH2
H2N NH2
N
CHO
OHC CHO
+
TPT-3NH2 TPA-3CHO
TPT-TPA COF (TPT-COF-4)
NN
N
N NN
N
NN
NN
NN
NN
NN
N
A mixture of TPT-3NH2 (70.0 mg, 0.200 mmol), TPA-3CHO (77.5 mg, 0.200 mmol), and
12
acetic acid (6 M, 1.2 mL) in 1,4-dioxane/mesitylene (5 mL/5 mL) in a Pyrex tube (25 mL) was
degassed using three freeze/pump/thaw cycles. The tube was sealed off under a flame and then
heated at 120 °C for 96 h. After cooling to room temperature, the yellow precipitate was washed
several times with THF, MeOH, and acetone, respectively, and then dried under vacuum at 120
°C overnight to yield a yellow solid (82%).
TPT-TPP COF (TPT-COF-5)
NN
N
NH2
H2N NH2
NN
N
N N
NN
NN
NN
NN
NN
NN
N
+
TPT-3NH2 TPP-3CHO
TPT-TPP COF (TPT-COF-5)
N
CHO
OHC CHO
A mixture of TPT-3NH2 (70.0 mg, 0.200 mmol), TPP-3CHO (77.3 mg, 0.200 mmol), and acetic
acid (6 M, 1.2 mL) in 1,4-dioxane/mesitylene (5 mL/5 mL) in a Pyrex tube (25 mL) was
degassed using three freeze/pump/thaw cycles. The tube was sealed off under a flame and then
heated at 120 °C for 96 h. After cooling to room temperature, the yellow precipitate was washed
several times with THF, MeOH, and acetone, respectively, and then dried under vacuum at 120
°C overnight to yield a yellow solid (86%).
13
TPT-TPT COF (TPT-COF-6)
NN
N
NH2
H2N NH2
NN
N
CHO
OHC CHO
NN
N
N N
NN N
N NN
NN
NN
NN
NN
NN
N NN
+
TPT-3CHO
TPT-TPT COF (TPT-COF-6)
TPT-3NH2
A mixture of TPT-3NH2 (70.0 mg, 0.200 mmol), TPT-3CHO (77.7 mg, 0.200 mmol), and acetic
acid (6 M, 1.2 mL) in 1,4-dioxane/mesitylene (5 mL/5 mL) in a Pyrex tube (25 mL) was
degassed using three freeze/pump/thaw cycles. The tube was sealed off under a flame and then
heated at 120 °C for 96 h. After cooling to room temperature, the yellow precipitate was washed
several times with THF, MeOH, and acetone, respectively, and then dried under vacuum at 120
°C overnight to yield a yellow solid (89%).
14
Section D. NMR spectral profiles
11.0 10.5 10.0 9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0
b a
Chemical shift (ppm)
N
NO2
O2N NO2
a b
Figure S1. 1H NMR spectrum of tris(4-nitrophenyl)amine (TPA-3NO2).
180 170 160 150 140 130 120 110 100
d
cb
a
Chemical shift (ppm)
N
NO2
O2N NO2
a b c
d
Figure S2. 13C NMR spectrum of tris(4-nitrophenyl)amine (TPA-3NO2).
15
10.0 9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0
c
b
Chemical shift (ppm)
N
NH2
H2N NH2
a b c
a
Figure S3. 1H NMR spectrum of tris(4-aminophenyl)amine(TPA-3NH2).
180 170 160 150 140 130 120 110 100
d
c
b
a
Chemical shift (ppm)
N
NH2
H2N NH2
a b c
d
Figure S4. 13C NMR spectrum of tris(4-aminophenyl)amine(TPA-3NH2).
16
10.0 9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0
c
ba
Chemical shift (ppm)
NN
N
NH2
H2N NH2
a bc
Figure S5. 1H NMR spectrum of 2,4,6-tris(4-aminophenyl)triazine (TPT-3NH2).
200 190 180 170 160 150 140 130 120 110 100
e
dc
ba
Chemical shift (ppm)
NN
N
NH2
H2N NH2
a b c de
Figure S6. 13C NMR spectrum of 2,4,6-tris(4-aminophenyl)triazine (TPT-3NH2).
17
12.0 11.5 11.0 10.5 10.0 9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0
cba
Chemical shift (ppm)
N
CHO
OHC CHO
a b c
Figure S7. 1H NMR spectrum of tris(4-formylphenyl)amine (TPA-3CHO).
220 210 200 190 180 170 160 150 140 130 120 110 100
e
d
cb
a
Chemical shift (ppm)
N
CHO
OHC CHO
a b c
de
Figure S8. 13C NMR spectrum of tris(4-formylphenyl)amine (TPA-3CHO).
18
10.0 9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0
CDCl3
d
a
b,c,e
Chemical shift (ppm)
N
Br
Br Br
abc
d e
Figure S9. 1H NMR spectrum of tris(4-bromophenyl)pyridine (TPP-3Br).
180 170 160 150 140 130 120 110 100
fd
jie
c
hb
g
a
Chemical shift (ppm)
N
Br
Br Br
a b cde
f
ghi j
Figure S10. 13C NMR spectrum of tris(4-bromophenyl)pyridine (TPP-3Br).
19
12.0 11.5 11.0 10.5 10.0 9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0
b
CDCl3
a,c,ef
d
Chemical shift (ppm)
N
CHO
OHC CHO
abc
d e f
Figure S11. 1H NMR spectrum of 2,4,6-tris(4-formylphenyl)pyridine (TPP-3CHO).
200 190 180 170 160 150 140 130 120 110 100
g
N
CHO
OHC CHO
abc def
g
hi j
k
lm
l
k j
i
mfh
e d
cb
a
Chemical shift (ppm)
Figure S12. 13C NMR spectrum of 2,4,6-tris(4-formylphenyl)pyridine (TPP-3CHO).
20
12.0 11.5 11.0 10.5 10.0 9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0
ba
CDCl3
Chemical shift (ppm)
NN
N
Br
Br Br
a b
Figure S13. 1H NMR spectrum of 2,4,6-tris(4-bromophenyl)-1,3,5-triazine (TPT-3Br).
180 170 160 150 140 130 120 110 100
c e d
ba
Chemical shift (ppm)
NN
N
Br
Br Br
a bd
c
e
Figure S14. 13C NMR spectrum of 2,4,6-tris(4-bromophenyl)-1,3,5-triazine (TPT-3Br).
21
12.0 11.5 11.0 10.5 10.0 9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0
CDCl3
cba
Chemical shift (ppm)
NN
N
CHO
OHC CHO
a b c
Figure S15. 1H NMR spectrum of 2,4,6-tris(4-formylphenyl)triazine (TPT-3CHO).
200 190 180 170 160 150 140 130 120 110 100
fe
dc
ba
Chemical shift (ppm)
NN
N
CHO
OHC CHO
ab
c d
ef
Figure S16. 13C NMR spectrum of 2,4,6-tris(4-formylphenyl)triazine (TPT-3CHO).
22
Section E. ESI
Figure S17. High-resolution FT mass spectrum of TPA-3NH2.
Figure S18. High-resolution FT mass spectrum of TPT-3NH2.
23
Figure S19. High-resolution FT mass spectrum of TPA-3CHO.
Figure S20. High-resolution FT mass spectrum of TPP-3CHO.
24
Figure
S21. FT-MS of TPT-3CHO.
25
Section F. FT-IR spectral profiles
4000 3500 3000 2500 2000 1500 1000 500
(C=C)(C=C)
(C=N)
(terminal C=O)
1495
1616
1701(terminal N-H) (terminal C-H)
3444, 3363
(C=C)
(C=C)(C=O)
(C=C)
(N-H bending)(aromatic C-H)
16203034, 3003
3406, 3334, 3207
N
NH2
H2N NH2
N
CHO
OHC CHO
1580
1504
1587
1504
(c)
(b)
Wavenumber (cm-1)
(a)
N
NN
(N-H)
2923, 2801, 2724(C-H)
1693
2924, 2851
(aromatic C-H)3020
Figure S22. FTIR spectra of (a) TPA-3NH2, (b) TPA-3CHO, and (c) TPA-TPA-COF (TPA-COF-1).
4000 3500 3000 2500 2000 1500 1000 500Wavenumber (cm-1)
N
NH2
H2N NH2
N
CHO
OHC CHO
(a)
(b)
(c)
N
N
N
(C=C)
(N-H bending)1620
1504
2920, 2810, 2724(C-H) (C=C)
(C=N)(C=O)
1571, 1544
15981697
(aromatic C-H)3034, 3003
3406, 3334, 3207(N-H)
(terminal N-H) (terminal C-H)3444, 3365 2924, 2851
3050(aromatic C-H)
(C=C)(C=C)
(C=N)
(terminal C=O)
1497
1618
1697
1596
Figure S23. FTIR spectra of (a) TPA-3NH2, (b) TPP-3CHO, and (c) TPA-TPP-COF (TPA-COF-2).
26
4000 3500 3000 2500 2000 1500 1000 500
1608(C=N)
Wavenumber (cm-1)
N
NH2
H2N NH2
NN
N
CHO
OHC CHO
(a)
(b)
(c)
N
N
N NN
(aromatic C-H)3034, 3003
3406, 3334, 3207(N-H)
(C=C)
(N-H bending)1620
1504
2922, 2821, 2821(C-H)
(C=C)(C=C)
(C=O)1583
15171706
(terminal N-H) (terminal C-H)3444, 3370 2915, 2849
(C=C)(C=C)
(C=N)
(terminal C=O)
1508, 1495
1620
1703
1578
(aromatic C-H)
Figure S24. FTIR spectra of (a) TPA-3NH2, (b) TPT-3CHO, and (c) TPA-TPT-COF (TPA-COF-3).
4000 3500 3000 2500 2000 1500 1000 500
(C=C)(C=C)
(C=C)
(C=N)
1587, 1580
1623
1579
Wavenumber (cm-1)
NN
N
NH2
H2N NH2
N
CHO
OHC CHO
(a)
(b)
(c)
NN
N
NN
2923, 2801, 2724(C-H)
(C=C)
(C=C)(C=O) 1504
15871693
(aromatic C-H)3031
3460, 3379, 3321, 3207(N-H)
1606(N-H bonding)
(C=C)1517
(terminal N-H)(terminal C-H)
3464, 33782924, 2851
(C=N)1627
1508
(terminal C=O)1697
(aromatic C-H)3020
Figure S25. FTIR spectra of (a) TPT-3NH2, (b) TPA-3CHO, and (c) TPT-TPA-COF (TPT-COF-4).
27
4000 3500 3000 2500 2000 1500 1000 500Wavenumber (cm-1)
NN
N
NH2
H2N NH2
N
CHO
OHC CHO
NN
N
N
N
(C=C)
(C=N)1623
1579
1606(N-H bonding)
(C=C)1517
(a)
(b)
(c)
(aromatic C-H)3031
3460, 3379, 3321, 3207(N-H)
2920, 2810, 2724(C-H) (C=C)
(C=N)(C=O)
1571, 1544
15981697
(terminal N-H) (terminal C-H)3475, 3380 2920, 2851
3030(aromatic C-H)
(C=C)(C=C)
(C=N)
(terminal C=O)
1512
16221697
1594, 1576
Figure S26. FTIR spectra of (a) TPT-3NH2, (b) TPP-3CHO, and (c) TPT-TPP-COF (TPT-COF-5).
4000 3500 3000 2500 2000 1500 1000 500Wavenumber (cm-1)
(a)
(b)
(c)
NN
N
N
N NN
NN
N
NH2
H2N NH2
NN
N
CHO
OHC CHO
(aromatic C-H)3031
3460, 3379, 3321, 3207(N-H)
(C=C)
(C=N)1623
1579
1606(N-H bonding)
(C=C)1517
2922, 2821, 2821(C-H)
1608(C=N)
(C=C)(C=C)
(C=O)1583
15171706
(terminal N-H) (terminal C-H)3466, 3378 2922, 2851
(aromatic C-H)3040
(C=C)(C=C)
(C=N)
(terminal C=O)
1508
1622
1699
15801598(C=C)
Figure S27. FTIR spectra of (a) TPT-3NH2, (b) TPT-3CHO, and (c) TPT-TPT-COF (TPT-COF-6).
28
Section G. Elemental analysis
Table S1. Elemental analyses of TPA-TPA-COF (TPA-COF-1), TPA-TPP-COF (TPA-COF-
2), TPA-TPT-COF (TPA-COF-3), TPT-TPA-COF (TPT-COF-4), TPT-TPP-COF (TPT-COF-
5), and TPT-TPT-COF (TPT-COF-6).
COFs C% H% N%
Calcd. 84.44 5.19 10.37TPA-COF-1
Found 77.69 5.17 11.70
Calcd. 85.71 4.98 9.30TPA-COF-2
Found 78.34 5.08 10.38
Calcd. 81.45 4.64 13.61TPA-COF-3
Found 73.93 4.75 14.02
Calcd. 81.45 4.64 13.61TPT-COF-4
Found 76.28 4.66 14.73
Calcd. 85.46 4.71 9.83TPT-COF-5
Found 80.02 4.30 13.74
Calcd. 81.60 4.40 14.00TPT-COF-6
Found 74.70 4.02 17.47
29
Section H. TGA profiles
100 200 300 400 500 600 7000
10
20
30
40
50
60
70
80
90
100
Weig
ht L
oss (
%)
Temperature (°C)
(a) TPA-COF-1: 510 oC (b) TPA-COF-2: 520 oC (c) TPA-COF-3: 531 oC (d) TPT-COF-4: 549 oC (e) TPT-COF-5: 553 oC (f) TPT-COF-6: 574 oC
Td at 10 wt% loss in N2
Figure S28. TGA curves of TPA-COF-1 (blue), TPA-COF-2 (purple), TPA-COF-3 (olive),
TPT-COF-4 (orange), TPT-COF-5 (red), and TPT-COF-6 (magenta).
Table S2. Values of Td10% , Tonset and char yields
TPA-
COF-1
TPA-
COF-2
TPA-
COF-3
TPT-
COF-4
TPT-
COF-5
TPT-
COF-6
Td10% (oC) 510 520 531 549 553 574
Tonset(oC) 475 485 503 539 541 554
Char yield (%) 58 67 58 55 49 61
30
Section I. PXRD patterns
Table S3. Fractional atomic coordinates for the unit cell of TPA-COF-1 with AA-stacking
Space group: P3 (No. 143)
a = b = 20.22971 Å, c = 4.68099 Å, , α = β = 90o γ = 120o
Rwp = 8.61%, Rp = 6.80%
N1 0.15606 0.84400 0.46788 C14 0.30196 0.71399 0.62933
N2 0.33333 0.66667 0.62719 C15 0.33380 0.77853 0.79678
N3 0.00000 0.00000 0.41036 C16 0.30280 0.82355 0.80415
C4 0.04176 0.96258 0.41828 H17 -0.03063 0.87501 0.13003
C5 0.01829 0.89725 0.26175 H18 0.03854 0.80949 0.15564
C6 0.05726 0.85980 0.27772 H19 0.19331 0.97562 0.73955
C7 0.11977 0.88613 0.45335 H20 0.12531 1.04035 0.70812
C8 0.14448 0.95236 0.60635 H21 0.22813 0.89626 0.81446
C9 0.10574 0.98999 0.58799 H22 0.15994 0.72683 0.33726
C10 0.20791 0.85370 0.64918 H23 0.21297 0.64655 0.33757
C11 0.23999 0.80564 0.63848 H24 0.38252 0.79372 0.92266
C12 0.20840 0.74164 0.46747 H25 0.32791 0.87243 0.93906
C13 0.23876 0.69603 0.46579
31
Table S4. Fractional atomic coordinates for the unit cell of TPA-COF-2 with AA-stacking
Space group: P1 (No. 1)
a = 21.37104 Å, b = 22.96124 Å, c = 3.76045 Å, , α = β = 90o γ = 120o
Rwp = 9.14%, Rp = 6.76%
N1 0.14587 0.86438 0.57900 C40 0.04065 0.17149 0.39727
N2 0.37085 0.72916 0.39912 C41 0.00840 0.10371 0.41046
N3 0.71974 0.85984 0.51793 C42 0.03506 0.07114 0.58174
N4 0.13777 0.27860 0.54500 C43 0.09539 0.10917 0.74164
N5 -0.99844 1.00040 0.59067 C44 0.12805 0.17702 0.72754
C6 0.03995 0.96750 0.59357 C45 0.82783 0.86731 0.40286
C7 0.01682 0.90768 0.75216 C46 0.89652 0.90214 0.42477
C8 0.05268 0.87518 0.74750 C47 0.92976 0.96273 0.58156
C9 0.11261 0.90132 0.58378 C48 0.89125 0.98625 0.72403
C10 0.13713 0.96176 0.42942 C49 0.82256 0.95149 0.70320
C11 0.10107 0.99410 0.43458 H50 -0.02983 0.88515 0.87317
C12 0.19861 0.87745 0.41692 H51 0.03358 0.82896 0.86969
C13 0.22604 0.83352 0.43097 H52 0.18359 0.98442 0.30319
C14 0.19362 0.77431 0.59933 H53 0.12126 1.04010 0.31407
C15 0.21911 0.73227 0.60033 H54 0.22277 0.91967 0.26261
C16 0.27763 0.74868 0.43287 H55 0.14856 0.76070 0.73037
C17 0.31075 0.80866 0.27149 H56 0.19358 0.68757 0.73704
C18 0.28502 0.85049 0.26907 H57 0.35575 0.82227 0.13963
C19 0.30462 0.70403 0.42230 H58 0.31073 0.89576 0.13659
C20 0.26323 0.63637 0.42383 H59 0.21044 0.61552 0.43790
C21 0.29029 0.59557 0.40360 H60 0.38049 0.59284 0.36713
32
C22 0.35881 0.62359 0.38136 H61 0.47305 0.64932 0.04975
C23 0.39907 0.69132 0.37806 H62 0.59291 0.70023 0.03790
C24 0.47174 0.72243 0.35935 H63 0.60965 0.85578 0.64074
C25 0.24722 0.52388 0.40186 H64 0.48919 0.80458 0.65529
C26 0.50211 0.69373 0.18478 H65 0.17303 0.52384 0.08909
C27 0.57066 0.72307 0.17533 H66 0.10289 0.40562 0.08034
C28 0.61018 0.78145 0.34054 H67 0.24076 0.38698 0.69741
C29 0.58005 0.81074 0.51099 H68 0.31033 0.50530 0.71342
C30 0.51148 0.78170 0.51834 H69 0.70322 0.79069 0.16710
C31 0.18778 0.49459 0.22770 H70 0.08268 0.29653 0.20972
C32 0.14793 0.42705 0.22055 H71 0.01751 0.19365 0.26380
C33 0.16662 0.38746 0.38748 H72 -0.03784 0.07674 0.28800
C34 0.22572 0.41657 0.56374 H73 0.11781 0.08648 0.87400
C35 0.26564 0.48411 0.57074 H74 0.17446 0.20528 0.85232
C36 0.68242 0.81085 0.33242 H75 0.80495 0.82090 0.28180
C37 0.12436 0.31622 0.37196 H76 0.92346 0.88115 0.32082
C38 0.79028 0.89248 0.53805 H77 0.91412 1.03239 0.84436
C39 0.10146 0.20884 0.55383 H78 0.79405 0.97080 0.81291
33
Table S5. Fractional atomic coordinates for the unit cell of TPA-COF-3 with AA-stacking
Space group: P3 (No. 143)
a = b = 22.01013 Å, c = 3.75035 Å, , α = β = 90o γ = 120o
Rwp = 10.66%, Rp = 7.68%
N1 0.14306 0.86208 1.06915 C14 0.27918 0.75038 0.94236
N2 0.26765 0.64087 0.94638 C15 0.31381 0.81284 0.79848
N3 -1.00000 1.00000 1.10282 C16 0.28655 0.85358 0.78808
C4 0.03785 0.96632 1.09885 C17 0.30741 0.70676 0.94655
C5 0.01447 0.90514 1.25260 H18 -0.03195 0.88194 1.37529
C6 0.04994 0.87216 1.24176 H19 0.03081 0.82505 1.36129
C7 0.10979 0.89914 1.07711 H20 0.18078 0.98399 0.79923
C8 0.13448 0.96073 0.92690 H21 0.11934 1.04047 0.82218
C9 0.09878 0.99348 0.93799 H22 0.22189 0.92064 0.76447
C10 0.19673 0.87673 0.91163 H23 0.14287 0.75447 1.18467
C11 0.22475 0.83310 0.92652 H24 0.18998 0.68206 1.19511
C12 0.19042 0.77098 1.07428 H25 0.36136 0.82935 0.68767
C13 0.21715 0.72975 1.07955 H26 0.31361 0.90104 0.67055
34
Table S6. Fractional atomic coordinates for the unit cell of TPT-COF-4 with AA-stacking
Space group: P3 (No. 143)
a = b = 22.95627 Å, c = 3.95771 Å, , α = β = 90o γ = 120o
Rwp = 11.87%, Rp = 9.82%
N1 0.16968 0.82226 -0.05888 C14 0.30492 0.70941 0.10553
N2 -2.03289 0.93380 0.87295 C15 0.33647 0.77075 0.26428
N3 0.33333 0.66667 0.10499 C16 0.30923 0.81156 0.26727
C4 0.06995 0.93081 -0.11732 C17 -2.06659 -0.03350 -0.12742
C5 0.04030 0.86538 -0.22406 H18 -0.00900 0.84122 -0.32332
C6 0.07433 0.83098 -0.20635 H19 0.05129 0.78075 -0.29091
C7 0.13776 0.86053 -0.07680 H20 0.21767 0.95150 0.11716
C8 0.16811 0.92642 0.02458 H21 0.15832 1.01157 0.08778
C9 0.13446 0.96119 0.00386 H22 0.24416 0.87860 0.27278
C10 0.22139 0.83589 0.11492 H23 0.17146 0.71565 -0.17733
C11 0.24956 0.79231 0.10869 H24 0.21834 0.64414 -0.17153
C12 0.21762 0.73154 -0.05210 H25 0.38277 0.78775 0.38295
C13 0.24490 0.69076 -0.05213 H26 0.33482 0.85821 0.39417
35
Table S7. Fractional atomic coordinates for the unit cell of TPT-COF-5 with AA-stacking
Space group: P1 (No. 1)
a = 24.75939 Å, b = 26.10230 Å, c = 3.53306 Å, , α = β = 90o γ = 120o
Rwp = 10.80%, Rp = 8.73%
N1 0.18730 0.80969 0.52417 C43 0.06250 0.12427 0.46889
N2 0.39348 0.68721 0.49933 C44 0.09493 0.09425 0.48053
N3 0.18847 0.28049 0.51826 C45 0.15802 0.12682 0.51229
N4 0.71339 0.81577 0.32136 C46 0.18782 0.18797 0.52630
N5 -0.99725 1.91119 1.41244 C47 0.81059 0.81581 0.29792
N6 -0.90675 1.99979 1.47633 C48 0.87348 0.84659 0.31687
N7 -0.99793 1.99927 1.41790 C49 0.90515 0.90777 0.35700
C8 0.09660 0.90782 0.47492 C50 0.87244 0.93753 0.36693
C9 0.06585 0.84681 0.42465 C51 0.80952 0.90659 0.34812
C10 0.09671 0.81577 0.44332 C52 -1.02826 0.94024 0.39409
C11 0.15855 0.84445 0.51484 C53 -0.93654 1.94055 1.45380
C12 0.18982 0.90554 0.56388 C54 -0.93728 2.02943 1.45839
C13 0.15902 0.93686 0.54442 H55 0.01793 0.82315 0.36796
C14 0.24205 0.82588 0.62923 H56 0.07254 0.76892 0.40103
C15 0.26443 0.78405 0.61364 H57 0.23775 0.92943 0.61340
C16 0.22685 0.72616 0.49401 H58 0.18390 0.98380 0.58420
C17 0.24855 0.68715 0.47284 H59 0.27189 0.86962 0.73202
C18 0.30841 0.70491 0.57477 H60 0.18087 0.71147 0.40927
C19 0.34593 0.76298 0.69437 H61 0.21876 0.64382 0.36351
C20 0.32415 0.80211 0.71417 H62 0.39214 0.77789 0.77494
C21 0.33299 0.66457 0.53966 H63 0.35392 0.84648 0.80850
36
C22 0.29528 0.60350 0.54546 H64 0.24793 0.58458 0.60770
C23 0.31930 0.56678 0.48083 H65 0.40042 0.56514 0.35112
C24 0.38149 0.59237 0.42288 H66 0.20217 0.50234 0.23460
C25 0.41893 0.65313 0.44934 H67 0.13855 0.39608 0.21870
C26 0.48557 0.68064 0.42871 H68 0.28393 0.37762 0.67665
C27 0.27995 0.50195 0.47366 H69 0.34682 0.48369 0.71363
C28 0.22030 0.47586 0.34032 H70 0.48932 0.60514 0.64038
C29 0.18399 0.41502 0.32748 H71 0.59821 0.65110 0.61287
C30 0.20662 0.37893 0.44383 H72 0.61052 0.81112 0.21860
C31 0.26588 0.40466 0.57967 H73 0.49997 0.76430 0.23280
C32 0.30199 0.46543 0.59678 H74 0.69751 0.73522 0.51510
C33 0.51458 0.64947 0.53569 H75 0.12345 0.29735 0.30080
C34 0.57718 0.67598 0.52513 H76 0.06572 0.20650 0.48117
C35 0.61246 0.73440 0.41273 H77 0.01383 0.10044 0.44908
C36 0.58400 0.76597 0.30767 H78 0.18419 0.10496 0.52490
C37 0.52110 0.73933 0.31649 H79 0.23638 0.21264 0.54955
C38 0.67860 0.76137 0.41567 H80 0.78784 0.76898 0.26078
C39 0.16817 0.31483 0.41769 H81 0.89746 0.82259 0.30120
C40 0.15556 0.21771 0.50613 H82 0.89553 0.98466 0.39494
C41 0.77805 0.84564 0.32235 H83 0.78480 0.92983 0.36221
C42 0.09238 0.18528 0.48312
37
Table S8. Fractional atomic coordinates for the unit cell of TPT-COF-6 with AA-stacking
Space group: P3 (No. 143)
a = b = 25.40160 Å, c = 3.50762 Å, , α = β = 90o γ = 120o
Rwp = 10.04%, Rp = 8.25%
N1 0.15567 0.83995 0.50893 C15 0.32178 0.80510 0.42394
N2 0.27385 0.64359 0.46693 C16 0.29787 0.84278 0.42168
N3 -2.02993 0.94002 1.52920 C17 0.31009 0.70334 0.46695
C4 0.06332 0.93693 0.52705 C18 -2.06042 -0.03027 0.52929
C5 0.03291 0.87462 0.49761 H19 -0.01507 0.84982 0.47642
C6 0.06422 0.84381 0.49265 H20 0.04037 0.79592 0.46843
C7 0.12619 0.87422 0.51492 H21 0.20450 0.96149 0.58097
C8 0.15685 0.93650 0.55035 H22 0.15025 1.01538 0.58248
C9 0.12567 0.96747 0.55463 H23 0.24243 0.90682 0.40816
C10 0.21218 0.86018 0.45980 H24 0.15191 0.73930 0.54043
C11 0.23651 0.81961 0.46320 H25 0.19359 0.67298 0.54246
C12 0.19937 0.75803 0.50679 H26 0.36928 0.82413 0.38993
C13 0.22319 0.72027 0.50747 H27 0.32730 0.89011 0.38686
C14 0.28472 0.74337 0.46627
38
TPA-COF-1 TPA-COF-2
TPA-COF-3 TPT-COF-4
TPT-COF-5 TPT-COF-6
Figure S29. Simulated structures of TPA-COFs to TPT-COFs (top views along the c axis and
down views along the a axis).
39
Section J. SEM analysis(A) (B) (C)
(D) (E) (F)
Figure S30. SEM images of the TPA-COFs: (A) TPA-TPA-COF (TPA-COF-1), (B) TPA-TPP-
COF (TPA-COF-2), and (C) TPA-TPT-COF (TPA-COF-3); and the TPT-COFs: (D) TPT-
TPA-COF (TPT-COF-4), (E) TPT-TPP-COF (TPT-COF-5), and (F) TPT-TPT-COF (TPT-
COF-6).
40
Section K. CO2 isosteric heats of adsorption
0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.60
10
20
30
40
50Q
st (K
J/m
ol)
CO2 adsorbed (mmol/g)
TPA-COF-1
R2 = 0.934Intercept = 16.05standard error = 0.217Residual sum of squars = 0.301
Figure S31. Isosteric heat of adsorption (Qst) for TPA-COF-1 obtained from the CO2 uptake
isotherms collected at 298 and 273 K.
41
0.0 0.2 0.4 0.6 0.8 1.0 1.20
10
20
30
40
50Q
st (K
J/m
ol)
CO2 adsorbed (mmol/g)
TPA-COF-2
R2 = 0.967Intercept = 26.17standard error = 0.212Residual sum of squars = 0.122
Figure S32. Isosteric heat of adsorption (Qst) for TPA-COF-2 obtained from the CO2 uptake
isotherms collected at 298 and 273 K.
42
0.0 0.2 0.4 0.6 0.8 1.00
10
20
30
40
50Q
st (K
J/m
ol)
CO2 adsorbed (mmol/g)
TPA-COF-3
R2 = 0.952Intercept = 28.38standard error = 0.358Residual sum of squars = 0.469
Figure S33. Isosteric heat of adsorption (Qst) for TPA-COF-3 obtained from the CO2 uptake
isotherms collected at 298 and 273 K.
43
0.0 0.2 0.4 0.6 0.8 1.00
10
20
30
40
50Q
st (K
J/m
ol)
CO2 adsorbed (mmol/g)
TPT-COF-4
R2 = 0.975Intercept = 10.06standard error = 0.048Residual sum of squars = 0.016
Figure S34. Isosteric heat of adsorption (Qst) for TPT-COF-4 obtained from the CO2 uptake
isotherms collected at 298 and 273 K.
44
0.0 0.2 0.4 0.6 0.8 1.00
10
20
30
40
50Q
st (K
J/m
ol)
CO2 adsorbed (mmol/g)
TPT-COF-5
R2 = 0.908Intercept = 18.69standard error = 0.797Residual sum of squars = 6.184
Figure S35. Isosteric heat of adsorption (Qst) for TPT-COF-5 obtained from the CO2 uptake
isotherms collected at 298 and 273 K.
45
0.0 0.2 0.4 0.6 0.8 1.0 1.20
10
20
30
40
50Q
st (K
J/m
ol)
CO2 adsorbed (mmol/g)
TPT-COF-6
R2 = 0.987Intercept = 33.14standard error = 0.484Residual sum of squars = 1.712
Figure S36. Isosteric heat of adsorption (Qst) for TPT-COF-6 obtained from the CO2 uptake
isotherms collected at 298 and 273 K.
46
Section L. Electrochemical analysis
Figure S37. CV traces of the COFs, recorded at various scan rates: (A) TPA-COF-1, (B) TPA-
COF-2, (C) TPA-COF-3, (D) TPT-COF-4, (E) TPT-COF-5, and (F) TPT-COF-6.
Recommended